US4469629A - Method for extracting fluoride ions from a nuclear fuel solution - Google Patents

Method for extracting fluoride ions from a nuclear fuel solution Download PDF

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Publication number
US4469629A
US4469629A US06/251,840 US25184081A US4469629A US 4469629 A US4469629 A US 4469629A US 25184081 A US25184081 A US 25184081A US 4469629 A US4469629 A US 4469629A
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United States
Prior art keywords
solution
nuclear fuel
solid phase
silica
hydrated silica
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Expired - Fee Related
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US06/251,840
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English (en)
Inventor
Leon E. J. Vandevelde
Leon H. J. M. Baetsle
Daniel J. G. Huys
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Centre dEtude de lEnergie Nucleaire CEN
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Centre dEtude de lEnergie Nucleaire CEN
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Assigned to CENTRE D`ETUDE DE 1`ENERGIE NUCLEAIRE, C.E.N., AVENUE PLASKY, 144- ETTERBEEK- BELGIUM A INSTITUT D`UTILITE PUBLIQUE OF BELGIAN LAWS reassignment CENTRE D`ETUDE DE 1`ENERGIE NUCLEAIRE, C.E.N., AVENUE PLASKY, 144- ETTERBEEK- BELGIUM A INSTITUT D`UTILITE PUBLIQUE OF BELGIAN LAWS ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BAETSLE, LEON H. J. M., HUYS, DANIEL J. G., VANDEVELDE, LEON E. J.
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/42—Reprocessing of irradiated fuel
    • G21C19/44—Reprocessing of irradiated fuel of irradiated solid fuel
    • G21C19/46—Aqueous processes, e.g. by using organic extraction means, including the regeneration of these means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • This invention relates to a method for extracting fluoride ions from a nuclear fuel solution, notably of UO 2 --, PuO 2 --, ThO 2 --type, discretely or in admixture, which is obtained by contacting said fuels with a mixture of HNO 3 and HF, before a purifying and extracting treatment of said fuels.
  • Such known extracting lies in complexing the fluorine with Al 3+ ions.
  • the complex thus formed precipitates and is separated by filtering. Said precipitate cannot however be recycled and does thus comprise a substantial contribution in solid radio-active wastes (see G. A. BURNEY ea., DP-1419 (1976)).
  • An essential object of this invention is to provide a new method for extracting fluoride ions from said solutions which allows to obviate the drawbacks of the known method which is both simple and efficient while resulting in a smaller amount of radio-active wastes.
  • said solution is treated with a solid phase from hydrated silica, such as silica gel and/or silicic acid, to bind the fluorine to the silicium, said solid phase then being separated from the solution.
  • a solid phase from hydrated silica such as silica gel and/or silicic acid
  • FIG. 1 is a diagram showing the influence of time on the lowering of the fluoride ion percentage in a nuclear fuel solution which has been treated with hydrated silica.
  • FIG. 2 shows the influence of the amount of hydrated silica being used, on the extracting of fluoride ions from a nuclear fuel solution, during 15 minutes.
  • the nuclear fuel to be re-treated is first contacted with a nitric acid solution to bring most of the fuel into solution, notably uranium oxide (UO 2 ).
  • a nitric acid solution to bring most of the fuel into solution, notably uranium oxide (UO 2 ).
  • Said solid portion is then dissolved by means of a mixture from HNO 3 and HF.
  • the solution from said 10% of nuclear fuel which thus contains fluoride ions with concentrations varying from 0.05 to 0.5 molar, according to the nature of the fuel to be dissolved, is then subjected to the method for extracting fluoride ions according to the invention.
  • said fluorinated solution which contains the completely dissolved nuclear fuel is contacted with hydrated silica which is formed by silica gel and/or silicic acid, and which is preferably finely powdered.
  • the fluorine forms a complex with the silica, H 2 SiF 6 or SiF 6 , depending on the relative amount of fluorine and silica being present.
  • part from said complex remains fixed to the solid phase, while the other part from said complex evaporates.
  • Said solid phase is then separated, for instance by centrifugating or filtering.
  • the fluorine content in the solution or liquid phase has changed from 0.1M to about 3.10 -3 M which corresponds to a 97% fluorine extraction.
  • Said liquid phase is then diluted with the nitric solution that does not contain any HF and which has been used to dissolve essentially the uranium oxide.
  • the nuclear fuel solution containing fluoride ions is treated by the solid phase from hydrated silica at a temperature lying between 15° C. and 50° C. and preferably at room temperature.
  • the main portion of the fluorine remains fixed to said solid phase in the form of the H 2 SiF 6 and/or SiF 4 complex.
  • the amount of hydrated silica being used is a function of the initial content in fluoride ions.
  • the solid phase separated from the solution after forming of the fluorinated complex is recycled for treating a fresh amount of solution that contains fluoride ions.
  • silica When however the regenerating is too difficult or when the fission product content in the hydrated silica becomes too large, said silica is discharged to a treatment known per se of radio-active wastes.
  • Said wastes may advantageously be used for preparing glass beads in a known method for treating high-activity wastes by vitrifying.
  • vapours from said complex which are formed during the extracting treatment or during the pyro-hydrolysis, are recovered in a basic solution, notably a solution from sodium hydroxide or carbonate.
  • the method may be applied continuously or discontinuously.
  • said hydrated silica may be fed to the dissolver even after complete dissolving of the nuclear fuels by the mixture from HNO 3 and HF. In such a case, no special apparatus is thus required.
  • a cartridge which contains hydrated silica As soon as said cartridge is saturated, it may be replaced with a fresh cartridge, while the first cartridge is regenerated by pyro-hydrolysis as mentioned above.
  • Said pyro-hydrolysis may for example be performed by passing superheated steam, for instance at a temperature from 120° to 150° C., over the hydrated silica loaded with fluoride ions, said steam which carries the silico-fluorinated complex then being washed by said basic solution.
  • the temperature has substantially no influence on the fluorine extraction with hydrated silica from a fluorinated nitric solution with 10M HNO 3 +0.1M HF.
  • Sample TB4 has undergone a heat treatment without adding hydrated silica. Analysis shows the HF content is not influenced by such treatment.
  • the reaction rate in the above-defined conditions is very high: after 15 minutes the reaction is substantially completed.
  • FIG. 1 shows along the Y-axis the fluorine concentration in moles per liter, and along the X-axis the reaction time.
  • the amount of silica being used was 3 g for a fluorinated nitric solution (10M HNO 3 +0.1M HF).
  • FIG. 2 shows the influence of the silica amount for a reaction duration of 15 minutes.
  • the diagram in FIG. 2 also shows along the Y-axis the content of fluorinated ions in the solution and along the X-axis, the amount of hydrated silica being used.
  • FIG. 3 is a block-diagram from a particular embodiment of the extraction method according to the invention.
  • the mixture was stirred by magnetic stirring, while the atmosphere inside the reaction vessel was swept out by an air stream. Said air together with the vapour carried along have been fed to a wash-bottle containing 10 ml from basic solution (0.5 mole NaOH).
  • the fluorine extraction rate did reach 97%.
  • FIG. 3 shows a block-diagram of the various steps in a particular embodiment of the method for extracting fluoride ions from a nuclear fuel solution.
  • the nuclear fuel 1 is contacted with a suitable mixture 2 from HNO 3 and HF inside a dissolver 3 where the fuel is brought into solution.
  • Said solution is then contacted with hydrated silica 4 inside a reactor 5, which might be merged with dissolver 3 or be comprised of a replaceable cartridge containing hydrated silica.
  • the fluorinated gases (SiF 4 and/or H 2 SiF 6 ) being formed are fed to a washer 6 where said gases are treated with a basic solution 7. Said solution loaded with fluorinated compounds then enters an evaporator 8 and the solid residue which is obtained therein is fed to an equipment 9 for treating radio-active wastes.
  • the solid phase loaded with fluoride ions is separated from the liquid phase inside a filter, centrifuge or similar separating device 10.
  • the solid phase is recycled to reactor 5, possibly after regenerating in 12.
  • the radio-active residue resulting from said regenerating is also fed to equipment 9.
  • Regenerating occurs by pyro-hydrolysis and the fluorinated gases being formed by such treatment are also fed to washer 6.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Plasma & Fusion (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Silicon Compounds (AREA)
  • Removal Of Specific Substances (AREA)
US06/251,840 1980-04-08 1981-04-08 Method for extracting fluoride ions from a nuclear fuel solution Expired - Fee Related US4469629A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8007836A FR2480019B1 (fr) 1980-04-08 1980-04-08 Procede d'extraction d'ions fluorure d'une solution de combustibles nucleaires
FR8007836 1980-04-08

Publications (1)

Publication Number Publication Date
US4469629A true US4469629A (en) 1984-09-04

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US06/251,840 Expired - Fee Related US4469629A (en) 1980-04-08 1981-04-08 Method for extracting fluoride ions from a nuclear fuel solution

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US (1) US4469629A (de)
BE (1) BE888279A (de)
DE (1) DE3114211C2 (de)
FR (1) FR2480019B1 (de)
GB (1) GB2074555B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4769180A (en) * 1986-04-04 1988-09-06 Doryokuro Kakunenryo Kaihatsu Jigyodan Process for separately recovering uranium and hydrofluoric acid from waste liquor containing uranium and fluorine

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07198894A (ja) * 1994-01-07 1995-08-01 Mitsubishi Nuclear Fuel Co Ltd 放射性廃液の処理法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846256A (en) * 1973-09-17 1974-11-05 Atomic Energy Commission Chemical trap
US3976759A (en) * 1974-12-30 1976-08-24 Texaco Inc. Process for removal of fluoride compounds from spent alkylation catalyst

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD67408A (de) *
US2819144A (en) * 1943-05-18 1958-01-07 Glenn T Seaborg Separation of plutonium from uranium and fission products by adsorption
FR2074812A1 (en) * 1970-01-30 1971-10-08 Commissariat Energie Atomique Nuclear fuel recovery - fixing fluorine ions during evaporation to avoid corrosion
DE2933502C2 (de) * 1979-08-18 1984-03-08 Nukem Gmbh, 6450 Hanau Verfahren zur Reinigung von fluorwasserstoff- und fluorhaltigen Abgasen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846256A (en) * 1973-09-17 1974-11-05 Atomic Energy Commission Chemical trap
US3976759A (en) * 1974-12-30 1976-08-24 Texaco Inc. Process for removal of fluoride compounds from spent alkylation catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Clark et al., "The Removal of Trace Contaminants from Recycle Nitric Acid," Nuclear Technology, vol. 53, May 1981, pp. 235-240.
Clark et al., The Removal of Trace Contaminants from Recycle Nitric Acid, Nuclear Technology, vol. 53, May 1981, pp. 235 240. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4769180A (en) * 1986-04-04 1988-09-06 Doryokuro Kakunenryo Kaihatsu Jigyodan Process for separately recovering uranium and hydrofluoric acid from waste liquor containing uranium and fluorine

Also Published As

Publication number Publication date
DE3114211C2 (de) 1986-06-05
FR2480019A1 (fr) 1981-10-09
GB2074555B (en) 1983-06-29
BE888279A (nl) 1981-07-31
FR2480019B1 (fr) 1986-11-14
DE3114211A1 (de) 1982-04-15
GB2074555A (en) 1981-11-04

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Owner name: CENTRE D`ETUDE DE 1`ENERGIE NUCLEAIRE, C.E.N., AVE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:VANDEVELDE, LEON E. J.;BAETSLE, LEON H. J. M.;HUYS, DANIEL J. G.;REEL/FRAME:004272/0642

Effective date: 19810212

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Effective date: 19880904